Monoazo dyestuffs



Pate'nted Sept. 3, 1940 2,213,697 PATENT OFFICE MONOAZO DYESTUFFS Richard Fleischhauer,

Frankfort-on-the-Main,

and Adolf Miiller, Fechenheim, Germany, assignors to General Aniline & Film Corporation, a corporation of Delaware No Drawing. Application June 11, 1938, Serial No. 213,192. In Germany June 12, 1937 4 Claims.

The present invention relates to monoazodyestuffs, more particularly to those of the general formula:

wherein A stands for a member selected from the group consisting of hydrogen, halogen and methyl, nitro and sulfonic acid groups and R stands for a member selected from the group consisting of the following two acylaminohydroxynaphthalene-sulfonic acid radicals:

and

wherein one Y stands for a hydroxy group and the other Ys stand for hydrogen, and X means a halogenated aliphatic radical containing at least two carbon atoms.

The new dyestuffs are obtained by combining the diazo compounds of o-aminophenols which may be substituted in the 4, 5 and fi-positions of the benzene nucleus by halogen, methyl, nitro and sulfonic acid groups, with an acylamino hydroxynaphthalene sulfonic acid corresponding to one of the following general formulae:

wherein X and Y have the above signification. The dyestuffs thus formed can be converted when fixed on animal fibers into metallic compounds of very good fastness properties. Especially valuable are the after-chromed dyeings, being distinguished by a particular fastness to fulling. Surprisingly they resist a fulling process carried out under strong conditions and in this surpass analogous o-,o'-dihydroxy azodyestuifs, containing other aliphatic radicals or the benzoyl radical. Moreover the new dyestuffs have a good levelling power and according to the aminohydroxynaphthalenes used as starting materials a good or very good fastness to light.

The aforesaid acylaminohydroxynaphthalenes may be prepared. by acting with chlorides or anhydrides of halogenated aliphatic carboxylic acids containing more than 2 carbon atoms, on various aminohydroxynaphthalenes or their sulfonic acids in the presence of acid binding agents such as sodium acetate, bicarbonate, chalk or sodium carbonate.

One may likewise act with the above halogenated fatty acid chlorides or anhydrides on 0,0- dihydroxy azodyestufis derived from aminohydroxynaphthalenes.

Particularly valuable are dyestuffs containing the radicle of halogenopropionic acids. One may likewise use the commercial mixtures obtained by acting with chlorine or bromine on propionic acid or butyric acid chloride, containing, according to the amount of halogen applied, highly halogenated fatty acid chlorides.

Example 1 16.8 parts of 4-methyl-6-nitro-2-aminophenol are diazotized in the usual manner and the diazo solution obtained is allowed to run into an aque ous solution of 33 parts of 2=-(p-chloropropionylamino) -8-naphthol-6-sulfonic acid containing an excess of sodium carbonate. The mixture is stirred, until the combination is complete. Then the dyestuff formed of the formula:

OH OH NaOaS bonate a blue color which is converted into a pink color by the addition of an acid.

By employing 4-chloro-6-nitro-2-aminophenol as diazo component for the above example somewhat more bluish-gray shades are obtained of likewise very good fastness to fulling and light, when aftertreated with chromium compounds.

Example 2 18.9 parts of 4-chloro-5-nitro 2-aminopheno1 are diazotized in the usual manner and the diazo solution obtained is combined with an aqueous solution of 33 parts of 2-(fi-chloropropionyl amino) -8-naphthol-6sulfonic acid containing an excess of sodium carbonate. The mixture is stirred, until the combination is complete. Then the dyestufi formed of the formula on OH OzN NaOaS pared by employing 5-nitro-2-aminophenol as diazocomponent yields greenish-gray shades of 'very good fastness to fulling and good fastness to light when afterchromed.

By combining the aforesaid diazocompounds with 1-(,c-chloropropionylamino) -5-naphthol-"I- sulfonic acid dyestuffs are formed which dye wool bright blue shades, when afterchromed, whereas 2- (c-chloropropionylamino) 5 naphthol-7-sulfonic acid employed as coupling component yields dyestuffs which dye wool gray shades fast to fulling when afterchromed.

Example 3 The diazo solution obtained by diazotizing 18.9 parts of 4-chloro-6-nitro-2-aminophenol in the usual manner is allowed to run into an aqueous solution of 33 parts of l-(c-chloropropionylamino) -3-naphthol-6-sulfonic acid containing an excess of sodium carbonate. When the combination is complete the dyestuff formed of the formula OH OH I 1 S O Na is separated and dried. It is a dark powder, soli'ible in waterand dyeing wool when afterchromed gray shades of very good fastness to Washing, fulling and light' and good levelling power. sulfuric acid With a reddish-violet color and in sodium carbonate solution with a blue color which is converted into red by the addition of an acid;

A similar dyestuff which yields on wool some- 3 what more reddish-gray shades when after The dyestuff dissolves in concentrated chromed is obtained by employing l-(fi-chloropropionylamino) -6-naphthol-3 -sulfonic acid as coupling component. 7

Further on there may be employed as coupling components 1 (,8 bromopropionylamino) 3 naphthol-G-sulfonic acid or substitution derivatives of 1-amino-3-naphtho1-6-sulfonic acid which are substituted in the amino group by radicles of chlorinated butyric acids, whereby similar dyestuffs of likewise good properties are obtained.

Example 4 22.4 parts of 4-chloro-2-aminophenol-6-sulfonic acid are diazotized in the usual manner and the diazo solution obtained is combined with an aqueous solution of 33 parts of l-(c-chloropropionylamino) -3-naphthol-6-sulfonic acid. When the combination is complete the dyestufi formed of the formula (I)H (RH I 1 S O Na is separated and dried. It is a dark powder. soluble in water and dyeing wool navy-blue shades of very good fastness to fulling and light when" afterchromed. The dyestuff dissolves in concentrated sulfuric acid with a red color.

By employing 4-chloro-2-aminophenol as diazocomponent a dyestulf is formed which dyes wool very reddish-blue shades of likewise very goodfastness to fulling and light when afterchromed.

Earamplc 5 The diazo solution obtained by diazotizing 18.9

parts of 4-chloro-5-nitro-2 -aminophenol in the usual manner is combined with an aqueous solu-' tion of 33 parts of l-(,c-chloropropionylamino)- 6-naphthol-3-sulfonic acid containing an excess of sodium carbonate. When the combination is complete, the dyestuff formed of 5 the formula OH on OzN NH-O o-on -om-oi o1 S03Na is separated and dried.

sodium carbonate solution with a pale violet color and in concentrated sulfuric acid with a red color. The dyestuff dyes wool bluish-gray shades of very good fastness to fulling and light when afterchromed.

Example 6 16.8 parts of 4-methyl-6enitro-2-aminopheno1 are diazotized in the usual manner and the diazo solution obtained is allowed to run into an aqueous solution of 33 parts of l-(B-chloropropionylamino) -7-naphthol-3-sulfonic acid containing an excess of sodium carbonate. stirred, until the combination is complete. Then the dyestuif formed of the formula s OzNa H It is a dark powder,. soluble in water with a reddish-blue color, in

The mixture is.

is separated and dried. It is a violet powder, soluble in water in the presence of sodium carbonate with a blue color and in the presence of acetic or mineral acid with a light red color, and in concentrated sulfuric acid with a bluishred color. The dyestuff dyes wool from an acid bath red shades which are converted when afterchromed into neutral-gray shades of very good fastness to fulling and light and of good levelling power.

By employing 4-sulfo-2-aminophenol as diazocomponent a dyestuff is obtained which dyes wool reddish-gray shades when afterchromed, whereas the dyestuffs obtained while using 4- chloro-6-nitro-2-aminophenol and 4-chloro-5- nitro-Z-aminophenol as diazo components yield more greenish-gray shades of similar good fastness properties when afterchromed.

By combining diazotized 4-chloro-2-aminophenol with the above coupling component a dyestufi is formed of the formula which is when dry a dark violet powder, soluble in water and dyeing wool when afterchromed reddish-gray shades of very good fastness to fulling and light and of good levelling power.

Example 7 15.4 parts of 5-nitro-2l-aminophenol are diazotized and the diazo solution obtained is allowed to run into an aqueous solution of 33 parts of 1-(/R-chloropropionylamino) '7 -naphthol- 4 sulfonic acid containing pyridine and sodium bicarbonate. The mixture is stirred until the combination is complete. Then the dyestuff formed of the formula NH-CO-GHr-CHs-Ol is separated and dried. It is a violet powder which dissolves in water in the presence of sodium carbonate with a blue color and in the presence of acetic or mineral acid with a bluishred color, and in concentrated sulfuric acid with a bluish-red color. The dyestuff dyes wool from an acid bath red shades which are converted into greenish-gray shades of excellent fastness to fulling and very good fastness to light when afterchromed.

We claim:

1. The monoazodyestufis of the general formula:

wherein A stands for a member selected from the group consisting of hydrogen, halogen and methyl, nitro and sulfonic acid groups and R stands for a member selected from the group consisting of the following two acylaminohydroxynaphthalene-sulfonic acid radicals:

which dyestufi is a dark-brown powder, soluble in water and dyeing wool, when afterchromed on the fiber, reddish-gray shades of very good fastness to fulling and light.

3. The monoazodyestuff of the formula SOzNa which dyestuff is a dark violet powder, soluble in water and dyeing wool, when afterchromed on the fiber, reddish-gray shades of very good fastness to fulling and light and of good levelling power.

4. The monoazodyestufi of the formula which dyestufi is a violet powder, soluble in water and dyeing wool, when afterchromed on the fiber, greenish-gray shades of excellent fastness to fulling and very good fastness to light.

-RICHARD lLEISCI-l'l-1AUER. ADOLF MULLER. 

